JPH0827206A - Method for producing vinyl chloride polymer - Google Patents
Method for producing vinyl chloride polymerInfo
- Publication number
- JPH0827206A JPH0827206A JP16209194A JP16209194A JPH0827206A JP H0827206 A JPH0827206 A JP H0827206A JP 16209194 A JP16209194 A JP 16209194A JP 16209194 A JP16209194 A JP 16209194A JP H0827206 A JPH0827206 A JP H0827206A
- Authority
- JP
- Japan
- Prior art keywords
- vinyl chloride
- group
- polymer
- vinyl
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 229920000642 polymer Polymers 0.000 title claims abstract description 33
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 23
- 239000000178 monomer Substances 0.000 claims abstract description 22
- 239000004094 surface-active agent Substances 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 9
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 9
- 239000012736 aqueous medium Substances 0.000 claims abstract description 5
- 125000003342 alkenyl group Chemical group 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- 125000005156 substituted alkylene group Chemical group 0.000 claims description 3
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 claims description 2
- 238000010557 suspension polymerization reaction Methods 0.000 claims 1
- 230000005484 gravity Effects 0.000 abstract description 11
- 229920000915 polyvinyl chloride Polymers 0.000 abstract description 5
- -1 heptenyl group Chemical group 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 5
- 230000002411 adverse Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 239000000375 suspending agent Substances 0.000 description 3
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 239000002216 antistatic agent Substances 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 125000003493 decenyl group Chemical group [H]C([*])=C([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000005066 dodecenyl group Chemical group C(=CCCCCCCCCCC)* 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000006038 hexenyl group Chemical group 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000005187 nonenyl group Chemical group C(=CCCCCCCC)* 0.000 description 2
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000005064 octadecenyl group Chemical group C(=CCCCCCCCCCCCCCCCC)* 0.000 description 2
- 125000004365 octenyl group Chemical group C(=CCCCCCC)* 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000005504 styryl group Chemical group 0.000 description 2
- 238000010558 suspension polymerization method Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 125000005063 tetradecenyl group Chemical group C(=CCCCCCCCCCCCC)* 0.000 description 2
- 125000005040 tridecenyl group Chemical group C(=CCCCCCCCCCCC)* 0.000 description 2
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000005065 undecenyl group Chemical group C(=CCCCCCCCCC)* 0.000 description 2
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 description 1
- UKDKWYQGLUUPBF-UHFFFAOYSA-N 1-ethenoxyhexadecane Chemical compound CCCCCCCCCCCCCCCCOC=C UKDKWYQGLUUPBF-UHFFFAOYSA-N 0.000 description 1
- UIERETOOQGIECD-UHFFFAOYSA-N Angelic acid Natural products CC=C(C)C(O)=O UIERETOOQGIECD-UHFFFAOYSA-N 0.000 description 1
- UUPWEGAONCOIFJ-UHFFFAOYSA-N CCCCC(CC)COC(=O)OOC(O)=O Chemical compound CCCCC(CC)COC(=O)OOC(O)=O UUPWEGAONCOIFJ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 229920001213 Polysorbate 20 Polymers 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- UQLDLKMNUJERMK-UHFFFAOYSA-L di(octadecanoyloxy)lead Chemical compound [Pb+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O UQLDLKMNUJERMK-UHFFFAOYSA-L 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 1
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 1
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 1
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- OCWMFVJKFWXKNZ-UHFFFAOYSA-L lead(2+);oxygen(2-);sulfate Chemical compound [O-2].[O-2].[O-2].[Pb+2].[Pb+2].[Pb+2].[Pb+2].[O-]S([O-])(=O)=O OCWMFVJKFWXKNZ-UHFFFAOYSA-L 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 description 1
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002455 scale inhibitor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Landscapes
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
(57)【要約】
【目的】 帯電による嵩比重の減少が起こりにくく、し
かも、良好な品質を有する塩化ビニル系重合体を製造で
きる方法を提供する。
【構成】 塩化ビニル単量体または塩化ビニルを主成分
とするビニル系単量体の混合物を水性媒体中で懸濁重合
し、塩化ビニル系重合体を製造するに際し、重合率が３
０％〜７０％で、所定の一般式で表される界面活性剤を
前記塩化ビニル単量体または塩化ビニルを主成分とする
ビニル系単量体の混合物１００重量部当たり０．００１
〜１．０重量部の割合で重合系に添加する塩化ビニル系
重合体の製造方法。(57) [Summary] [Object] To provide a method for producing a vinyl chloride-based polymer having good quality, which is less likely to cause a decrease in bulk specific gravity due to electrification. [Structure] When a vinyl chloride monomer or a mixture of vinyl-based monomers having vinyl chloride as a main component is suspension-polymerized in an aqueous medium to produce a vinyl chloride-based polymer, the polymerization rate is 3%.
0% to 70% of the surfactant represented by the general formula 0.001 per 100 parts by weight of the vinyl chloride monomer or a mixture of vinyl monomers containing vinyl chloride as a main component.
A method for producing a vinyl chloride polymer, which is added to the polymerization system in an amount of from 1.0 to 1.0 part by weight.
Description
【０００１】[0001]
【産業上の利用分野】本発明は、懸濁重合法により塩化
ビニル系重合体を製造する方法に関し、特に、優れた流
動性を有する塩化ビニル系重合体の製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a vinyl chloride polymer by a suspension polymerization method, and more particularly to a method for producing a vinyl chloride polymer having excellent fluidity.
【０００２】[0002]
【従来の技術】塩化ビニル系重合体は、通常、懸濁重合
法によって製造され、スラリーからの分離、乾燥等の精
製の後、空気輸送により搬送後保管され、あるいは袋詰
めされる。2. Description of the Related Art Vinyl chloride polymers are usually produced by a suspension polymerization method, purified by separation from a slurry, dried, etc., transported by air transportation and then stored or packed.
【０００３】ところが、このようにして得られた塩化ビ
ニル系重合体は、搬送や袋詰の過程でそれ自体および他
の物との摩擦により静電気を帯び流動性が低下し、製造
直後の塩化ビニル系重合体に比べて嵩比重が減少するた
め、著しく取り扱いにくくなり、作業に重大な支障をき
たすという問題がある。このような重合体の帯電による
悪影響を低減する方法として、従来、帯電防止剤である
非イオン系界面活性剤またはカチオン系界面活性剤等を
塩化ビニル系重合体に添加する方法やスチームを塩化ビ
ニル重合体に吹込んで湿度を調整する方法が用いられて
きた。However, the vinyl chloride-based polymer thus obtained is charged with static electricity due to friction with itself and other substances during transport and bagging, and its fluidity is lowered. Since the bulk specific gravity is reduced as compared with the system polymer, there is a problem that it becomes extremely difficult to handle and seriously hinders work. As a method for reducing the adverse effect of such polymer charging, conventionally, a method of adding a nonionic surfactant or a cationic surfactant, which is an antistatic agent, to a vinyl chloride polymer or steam is added to vinyl chloride. Methods have been used to adjust the humidity by blowing into the polymer.
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、上記の
界面活性剤を添加する方法は、重合体の嵩比重の減少を
十分に防止することができず、さらに製品の熱安定性お
よび初期着色性に悪影響を与えるという欠点を有してい
る。また、スチームを吹込む方法では必要な労働力の増
加、設備の複雑化等を招くという欠点を有している。However, the method of adding the above-mentioned surfactant cannot sufficiently prevent the decrease of the bulk specific gravity of the polymer, and further the thermal stability and the initial colorability of the product. It has the drawback of having an adverse effect. Further, the method of blowing steam has drawbacks such as an increase in required labor force and complication of equipment.
【０００５】本発明は上記の問題点に鑑みてなされたも
のであり、その目的は、帯電による嵩比重の減少が起こ
りにくく、しかも、良好な品質を有する塩化ビニル系重
合体を製造する方法を提供することにある。The present invention has been made in view of the above problems, and an object of the present invention is to provide a method for producing a vinyl chloride polymer having good quality, which is unlikely to cause a decrease in bulk specific gravity due to electrification. To provide.
【０００６】[0006]
【課題を解決するための手段】本発明は、上記目的を達
成するために鋭意検討を行なった結果、本発明を完成す
るに至ったものである。すなわち、本発明は、塩化ビニ
ル単量体または塩化ビニルを主成分とするビニル系単量
体の混合物を水性媒体中で懸濁重合し、塩化ビニル系重
合体を製造するに際し、重合率が３０％〜７０％で、下
記一般式（Ｉ）または一般式（ＩＩ）で表される界面活
性剤を前記塩化ビニル単量体または塩化ビニルを主成分
とするビニル系単量体の混合物１００重量部当たり０．
００１〜１．０重量部の割合で重合系に添加する塩化ビ
ニル系重合体の製造方法を提供するものである。DISCLOSURE OF THE INVENTION The present invention has been completed as a result of intensive studies to achieve the above object. That is, in the present invention, when a vinyl chloride polymer or a mixture of vinyl-based monomers containing vinyl chloride as a main component is suspension-polymerized in an aqueous medium to produce a vinyl chloride-based polymer, the polymerization rate is 30%. % -70%, and 100 parts by weight of the vinyl chloride monomer or a vinyl-based monomer containing vinyl chloride as a main component, the surfactant represented by the following general formula (I) or general formula (II). 0.
The present invention provides a method for producing a vinyl chloride polymer, which is added to a polymerization system at a ratio of 001 to 1.0 part by weight.
【０００７】[0007]
【化２】 Embedded image
【０００８】（式中、Ｒ1は炭素数６〜１８のアルキル
基、アルケニル基もしくはアラルキル基、Ｒ2は水素ま
たは炭素数６〜１８のアルキル基、アルケニル基もしく
はアラルキル基、Ｒ3は水素またはプロペニル基、Ａは
炭素数２〜４のアルキレン基または置換アルキレン基、
ｎは５〜２００の整数である。）以下、本発明をさらに
詳細に説明する。(Wherein R 1 is an alkyl group, alkenyl group or aralkyl group having 6 to 18 carbon atoms, R 2 is hydrogen or an alkyl group, alkenyl group or aralkyl group having 6 to 18 carbon atoms, R 3 is hydrogen or A propenyl group, A is an alkylene group having 2 to 4 carbon atoms or a substituted alkylene group,
n is an integer of 5 to 200. ) Hereinafter, the present invention will be described in more detail.
【０００９】本発明では、上記一般式（Ｉ）または一般
式（ＩＩ）で表される界面活性剤を用いるものである。In the present invention, the surfactant represented by the above general formula (I) or general formula (II) is used.
【００１０】ここに、上記一般式（Ｉ）または一般式
（ＩＩ）における、置換基Ｒ1は炭素数６〜１８のアル
キル基、アルケニル基またはアラルキル基である。アル
キル基としては、例えば、ヘキシル基、ヘプチル基、オ
クチル基、ノニル基、デシル基、ウンデシル基、ドデシ
ル基、トリデシル基、テトラデシル基、ペンタデシル
基、ヘキサデシル基、ヘプタデシル基、オクタデシル基
等があげられる。また、アルケニル基としては、例え
ば、ヘキセニル基、ヘプテニル基、オクテニル基、ノネ
ニル基、デセニル基、ウンデセニル基、ドデセニル基、
トリデセニル基、テトラデセニル基、ペンタデセニル
基、ヘキサデセニル基、ヘプタデセニル基、オクタデセ
ニル基等があげられる。さらに、アラルキル基として
は、例えば、スチリル基、ベンジル基、クミル基等があ
げられる。The substituent R 1 in the above general formula (I) or general formula (II) is an alkyl group, alkenyl group or aralkyl group having 6 to 18 carbon atoms. Examples of the alkyl group include a hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group and the like. Further, as the alkenyl group, for example, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group, an undecenyl group, a dodecenyl group,
Examples thereof include tridecenyl group, tetradecenyl group, pentadecenyl group, hexadecenyl group, heptadecenyl group and octadecenyl group. Further, examples of the aralkyl group include a styryl group, a benzyl group, a cumyl group and the like.
【００１１】次に、置換基Ｒ2は、水素または炭素数６
〜１８のアルキル基、アルケニル基またはアラルキル基
である。ここに、アルキル基としては、例えば、ヘキシ
ル基、ヘプチル基、オクチル基、ノニル基、デシル基、
ウンデシル基、ドデシル基、トリデシル基、テトラデシ
ル基、ペンタデシル基、ヘキサデシル基、ヘプタデシル
基、オクタデシル基等があげられる。また、アルケニル
基としては、例えば、ヘキセニル基、ヘプテニル基、オ
クテニル基、ノネニル基、デセニル基、ウンデセニル
基、ドデセニル基、トリデセニル基、テトラデセニル
基、ペンタデセニル基、ヘキサデセニル基、ヘプタデセ
ニル基、オクタデセニル基等があげられる。さらに、ア
ラルキル基としては、例えば、スチリル基、ベンジル
基、クミル基等があげられる。Next, the substituent R 2 is hydrogen or has 6 carbon atoms.
~ 18 alkyl, alkenyl or aralkyl groups. Here, as the alkyl group, for example, hexyl group, heptyl group, octyl group, nonyl group, decyl group,
Examples thereof include an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group and an octadecyl group. Examples of the alkenyl group include a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group, an undecenyl group, a dodecenyl group, a tridecenyl group, a tetradecenyl group, a pentadecenyl group, a hexadecenyl group, a heptadecenyl group and an octadecenyl group. To be Further, examples of the aralkyl group include a styryl group, a benzyl group, a cumyl group and the like.
【００１２】さらに、置換基Ａは、炭素数２〜４のアル
キレン基または置換アルキレン基を意味し、例えば、エ
チレン基、プロピレン基、ブチレン基、イソブチレン基
等の単独またはホモポリマーまたはブロックポリマーも
しくはランダムポリマーあるいはそれらの混合物でもよ
い。重合数ｎは５〜２００の整数であり、好ましくは１
０〜１００の範囲である。Further, the substituent A means an alkylene group having 2 to 4 carbon atoms or a substituted alkylene group, for example, an ethylene group, a propylene group, a butylene group, an isobutylene group or the like, a homopolymer, a block polymer or a random polymer. It may be a polymer or a mixture thereof. The number of polymerizations n is an integer of 5 to 200, preferably 1
It is in the range of 0 to 100.
【００１３】当該界面活性剤は、塩化ビニル単量体また
は塩化ビニルを主成分とするビニル系単量体の混合物１
００重量部当たり０．００１〜１．０重量部の割合で重
合系に添加することが必要である。その添加量が０．０
０１重量部未満であると帯電によるかさ比重の極端な低
下を防止できない。また、添加量が１．０重量部を超え
ても添加の効果はそれ以上高まらないので経済的ではな
い。The surfactant is a vinyl chloride monomer or a mixture 1 of vinyl monomers containing vinyl chloride as a main component.
It is necessary to add 0.001 to 1.0 part by weight to 00 parts by weight to the polymerization system. The amount added is 0.0
If the amount is less than 01 parts by weight, it is not possible to prevent the bulk specific gravity from extremely decreasing due to charging. Further, even if the amount added exceeds 1.0 part by weight, the effect of the addition does not increase any more, which is not economical.
【００１４】当該界面活性剤の添加時期は、反応系の重
合率が３０％〜７０％で行う。３０％未満の重合率で添
加すると重合体の粒子形成に悪影響を与えるので好まし
くない。また、７０％以上の重合率で添加すると水媒体
中への当該界面活性剤の残存量が多く帯電によるかさ比
重の極端な低下を防止できない。The surfactant is added at a polymerization rate of 30% to 70% in the reaction system. Addition at a polymerization rate of less than 30% is not preferable because it adversely affects the formation of polymer particles. If added at a polymerization rate of 70% or more, a large amount of the surfactant remains in the aqueous medium, and it is impossible to prevent an extreme decrease in bulk specific gravity due to charging.
【００１５】当該界面活性剤の重合系へ仕込む場合、そ
のまま仕込んでも良いが、溶剤で希釈したり水に分散さ
せてから仕込んでもよい。When the surfactant is charged into the polymerization system, it may be charged as it is, or it may be diluted with a solvent or dispersed in water before charging.
【００１６】塩化ビニル系重合体の単量体原料は、塩化
ビニル単量体単独または５０重量％以上の塩化ビニル単
量体と塩化ビニル単量体に共重合可能なビニル系単量体
との混合物である。塩化ビニルと共重合可能なビニル系
単量体としては、例えば、酢酸ビニルのようなアルキル
ビニルエステル、セチルビニルエーテルのようなアルキ
ルビニルエーテル、エチレンまたはプロピレンなどのα
−モノオレフィン系単量体、アクリル酸メチルのような
アクリル酸アルキルエステル、メタクリル酸メチルのよ
うなメタクリル酸アルキルエステル等があげられる。The monomer raw material of the vinyl chloride-based polymer is a vinyl chloride monomer alone or 50% by weight or more of a vinyl chloride monomer and a vinyl-based monomer copolymerizable with the vinyl chloride monomer. It is a mixture. Examples of vinyl monomers copolymerizable with vinyl chloride include alkyl vinyl esters such as vinyl acetate, alkyl vinyl ethers such as cetyl vinyl ether, and α such as ethylene or propylene.
-Monoolefin monomers, alkyl acrylates such as methyl acrylate, and methacrylic acid alkyl esters such as methyl methacrylate.
【００１７】また、本発明の製造方法では、従来から塩
化ビニル系重合体の製造方法に使用されている懸濁剤お
よび重合開始剤を用いることができる。Further, in the production method of the present invention, a suspending agent and a polymerization initiator which have hitherto been used in the production method of a vinyl chloride polymer can be used.
【００１８】懸濁剤としては、例えば、メチルセルロー
ス、エチルセルロース、ヒドロキシエチルセルロース、
ヒドロキシプロピルセルロースおよびヒドロキシプロピ
ルメチルセルロースのような水溶性セルロースエーテ
ル、水溶性または油溶性の部分ケン化ポリビニルアルコ
ール、アクリル酸重合体、ゼラチンのような水溶性ポリ
マーなどがある。これらは１種または２種以上組み合わ
せて使用する。Examples of the suspending agent include methyl cellulose, ethyl cellulose, hydroxyethyl cellulose,
There are water-soluble cellulose ethers such as hydroxypropyl cellulose and hydroxypropylmethyl cellulose, water-soluble or oil-soluble partially saponified polyvinyl alcohol, acrylic acid polymers, water-soluble polymers such as gelatin, and the like. These are used alone or in combination of two or more.
【００１９】重合の際、重合器への水性媒体、塩化ビニ
ルまたは塩化ビニルを含む単量体混合物、懸濁剤、重合
開始剤などの仕込み方法、仕込み割合、重合温度などの
種々の重合条件は従来と同様にして行えばよい。At the time of polymerization, various polymerization conditions such as an aqueous medium, vinyl chloride or a monomer mixture containing vinyl chloride, a suspending agent, a polymerization initiator, etc., a charging method, a charging ratio, a polymerization temperature and the like are set in the polymerization vessel. It may be performed in the same manner as the conventional one.
【００２０】本発明の製造方法では、必要に応じて塩化
ビニル系重合体の製造に使用される連鎖移動剤やｐＨ調
整剤、抗酸化剤、帯電防止剤、架橋剤、安定剤、充填
剤、スケール防止剤などを添加することもできる。In the production method of the present invention, a chain transfer agent, a pH adjusting agent, an antioxidant, an antistatic agent, a cross-linking agent, a stabilizer, a filler, which is used for producing a vinyl chloride polymer, if necessary. It is also possible to add a scale inhibitor or the like.
【００２１】[0021]
【実施例】以下、本発明を実施例によって具体的に説明
するが、本発明はこれらに限定されるものではない。EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto.
【００２２】実施例１〜３ ステンレス製重合器に、塩化ビニル単量体１００重量
部、脱イオン水１５０重量部、部分鹸化ポリビニルアル
コール０．１重量部、および２−エチルヘキシルパーオ
キシジカーボネート０．０４重量部を仕込み、温度５７
℃で重合を行った。重合率が５０％に達した時点で、表
１に示すそれぞれの界面活性剤を０．０５重量部添加
し、さらに重合を続けた。重合器内の圧力が６．０ｋｇ
／ｃｍ2Ｇに達した時点で反応を停止し、未反応の塩化
ビニル単量体を回収した後、脱水・乾燥して塩化ビニル
重合体を得た。Examples 1 to 3 In a stainless steel polymerization vessel, 100 parts by weight of vinyl chloride monomer, 150 parts by weight of deionized water, 0.1 part by weight of partially saponified polyvinyl alcohol, and 0.2 parts of 2-ethylhexyl peroxydicarbonate were added. Charge 04 parts by weight, temperature 57
Polymerization was carried out at ° C. When the polymerization rate reached 50%, 0.05 part by weight of each surfactant shown in Table 1 was added, and the polymerization was further continued. The pressure in the polymerization vessel is 6.0 kg
The reaction was stopped when the amount reached / cm 2 G, the unreacted vinyl chloride monomer was recovered, dehydrated and dried to obtain a vinyl chloride polymer.
【００２３】実施例４ 界面活性剤の添加量を０．０１重量部にした以外は実施
例１と同様にして塩化ビニル重合体を得た。Example 4 A vinyl chloride polymer was obtained in the same manner as in Example 1 except that the amount of the surfactant added was 0.01 part by weight.
【００２４】実施例５ 界面活性剤の添加量を０．８重量部にした以外は実施例
１と同様にして塩化ビニル重合体を得た。Example 5 A vinyl chloride polymer was obtained in the same manner as in Example 1 except that the amount of the surfactant added was 0.8 parts by weight.
【００２５】比較例１ 実施例１において、界面活性剤を添加しない以外は、実
施例１と同様にして塩化ビニル重合体を得た。Comparative Example 1 A vinyl chloride polymer was obtained in the same manner as in Example 1 except that the surfactant was not added.
【００２６】比較例２ 実施例１において、界面活性剤の代わりにポリオキシエ
チレンソルビタンモノラウレートを用いた以外は、実施
例１と同様にして塩化ビニル重合体を得た。Comparative Example 2 A vinyl chloride polymer was obtained in the same manner as in Example 1 except that polyoxyethylene sorbitan monolaurate was used instead of the surfactant.
【００２７】比較例３ 界面活性剤の添加量を０．０００５重量部にした以外は
実施例１と同様にして塩化ビニル重合体を得た。Comparative Example 3 A vinyl chloride polymer was obtained in the same manner as in Example 1 except that the amount of the surfactant added was 0.0005 parts by weight.
【００２８】比較例４ 実施例１において、界面活性剤の添加時期を重合率２０
％とした以外は、実施例１と同様にして重合を行った
が、粒子径が３００μｍ以上の粗大粒子が生成し評価に
値する重合体を得ることができなかった。Comparative Example 4 In Example 1, the surfactant was added at a polymerization rate of 20.
Polymerization was performed in the same manner as in Example 1 except that the content was changed to 100%, but coarse particles having a particle size of 300 μm or more were generated, and a polymer worthy of evaluation could not be obtained.
【００２９】上記の実施例１〜５および比較例１〜４で
得られた塩化ビニル重合体について、下記に示す方法で
かさ比重測定試験および熱安定性試験を行った。その結
果を表１および表２に示す。The vinyl chloride polymers obtained in Examples 1 to 5 and Comparative Examples 1 to 4 were subjected to a bulk specific gravity measurement test and a thermal stability test by the methods described below. The results are shown in Tables 1 and 2.
【００３０】[0030]
【表１】 [Table 1]
【００３１】[0031]
【表２】 [Table 2]
【００３２】＜かさ比重測定試験＞塩化ビニル重合体を
温度２３℃、相対湿度５０％の恒温恒湿室内に４８時間
放置した後、かさ比重をＪＩＳ Ｋ−６７２１の方法に
より測定した。<Bulk Specific Gravity Measurement Test> The vinyl chloride polymer was allowed to stand in a constant temperature and humidity chamber at a temperature of 23 ° C. and a relative humidity of 50% for 48 hours, and then the bulk specific gravity was measured by the method of JIS K-6721.
【００３３】また、上記と同様な条件で４８時間放置し
た塩化ビニル重合体を、ブラベンダープラネタリーミキ
サーで６０ｒｐｍ、２分間撹拌後、上記と同じ方法でか
さ比重を比較した。The vinyl chloride polymer left under the same conditions as above for 48 hours was stirred at 60 rpm for 2 minutes with a Brabender planetary mixer, and the bulk specific gravity was compared by the same method as above.
【００３４】＜熱安定性試験＞塩化ビニル重合体１００
重量部に対して、 三塩基性硫酸鉛 １．０重量部 ステアリン酸鉛 １．５ 〃 ステアリン酸カルシウム ０．５ 〃 を配合し、１９０℃のロールで５分間混練した後、暑さ
１ｍｍのシートを作成し、このシートを１９０℃のオー
ブンに入れて黒化するまでの時間を測定した。<Thermal stability test> Vinyl chloride polymer 100
1 part by weight of tribasic lead sulfate 1.0 part by weight of lead stearate 1.5 〃 calcium stearate 0.5 〃 are mixed, and after kneading for 5 minutes with a roll at 190 ° C, a sheet with a heat of 1 mm is prepared. The sheet was prepared and placed in an oven at 190 ° C., and the time until blackening was measured.
【００３５】[0035]
【発明の効果】上記の説明から明らかなように、本発明
の方法によると、帯電による嵩比重の減少が起こりにく
く、しかも、良好な品質を有する塩化ビニル系重合体を
製造できる効果を有するものである。As is apparent from the above description, according to the method of the present invention, it is possible to produce a vinyl chloride polymer having good quality, which is unlikely to cause a decrease in bulk specific gravity due to electrification. Is.
Claims (1)
成分とするビニル系単量体の混合物を水性媒体中で懸濁
重合し、塩化ビニル系重合体を製造するに際し、重合率
が３０％〜７０％で、下記一般式（Ｉ）または一般式
（ＩＩ）で表される界面活性剤を前記塩化ビニル単量体
または塩化ビニルを主成分とするビニル系単量体の混合
物１００重量部当たり０．００１〜１．０重量部の割合
で重合系に添加することを特徴とする塩化ビニル系重合
体の製造方法。 【化１】 （式中、Ｒ1は炭素数６〜１８のアルキル基、アルケニ
ル基またはアラルキル基、Ｒ2は水素または炭素数６〜
１８のアルキル基、アルケニル基もしくはアラルキル
基、Ｒ3は水素またはプロペニル基、Ａは炭素数２〜４
のアルキレン基または置換アルキレン基、ｎは５〜２０
０の整数である。）1. When a vinyl chloride polymer is produced by suspension polymerization of a vinyl chloride monomer or a mixture of vinyl monomers containing vinyl chloride as a main component in an aqueous medium, the polymerization rate is 30%. % To 70% of the surfactant represented by the following general formula (I) or general formula (II) per 100 parts by weight of the vinyl chloride monomer or the vinyl-based monomer mixture containing vinyl chloride as a main component. A method for producing a vinyl chloride polymer, which comprises adding 0.001 to 1.0 part by weight to a polymerization system. Embedded image (In the formula, R 1 is an alkyl group having 6 to 18 carbon atoms, an alkenyl group or an aralkyl group, and R 2 is hydrogen or having 6 to 18 carbon atoms.
18 alkyl group, alkenyl group or aralkyl group, R 3 is hydrogen or propenyl group, A is C 2-4
Alkylene group or substituted alkylene group, n is 5 to 20
It is an integer of 0. )
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16209194A JPH0827206A (en) | 1994-07-14 | 1994-07-14 | Method for producing vinyl chloride polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16209194A JPH0827206A (en) | 1994-07-14 | 1994-07-14 | Method for producing vinyl chloride polymer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0827206A true JPH0827206A (en) | 1996-01-30 |
Family
ID=15747910
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16209194A Pending JPH0827206A (en) | 1994-07-14 | 1994-07-14 | Method for producing vinyl chloride polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0827206A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7109275B2 (en) | 2002-04-12 | 2006-09-19 | Akzo Nobel N.V. | Co-metering of organic initiators and protective colloids during polymerization reactions |
| JP2011207999A (en) * | 2010-03-30 | 2011-10-20 | Sekisui Plastics Co Ltd | Non-spherical polymer particle and method for producing the same |
-
1994
- 1994-07-14 JP JP16209194A patent/JPH0827206A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7109275B2 (en) | 2002-04-12 | 2006-09-19 | Akzo Nobel N.V. | Co-metering of organic initiators and protective colloids during polymerization reactions |
| JP2011207999A (en) * | 2010-03-30 | 2011-10-20 | Sekisui Plastics Co Ltd | Non-spherical polymer particle and method for producing the same |
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